Toyohiko J. Konno

The demonstration of significant ferroelectricity in epitaxial Y-doped HfO2 film.

Ferroelectricity and Curie temperature are demonstrated for epitaxial Y-doped HfO2 film grown on (110) yttrium oxide-stabilized zirconium oxide (YSZ) single crystal using Sn-doped In2O3 (ITO) as bottom electrodes. The XRD measurements for epitaxial film enabled us to investigate its detailed crystal structure including orientations of the film. The ferroelectricity was confirmed by electric displacement filed – electric filed hysteresis measurement, which revealed saturated polarization of 16u2009μC/cm2. Estimated spontaneous polarization based on the obtained saturation polarization and the crystal structure analysis was 45u2009μC/cm2. This value is the first experimental estimations of the spontaneous polarization and is in good agreement with the theoretical value from first principle calculation. Curie temperature was also estimated to be about 450u2009°C. This study strongly suggests that the HfO2-based materials are promising for various ferroelectric applications because of their comparable ferroelectric properties including polarization and Curie temperature to conventional ferroelectric materials together with the reported excellent scalability in thickness and compatibility with practical manufacturing processes.

Orientation control and domain structure analysis of {100}-oriented epitaxial ferroelectric orthorhombic HfO2-based thin films

Orientation control of {100}-oriented epitaxial orthorhombic 0.07YO1.5-0.93HfO2 films grown by pulsed laser deposition was investigated. To achieve in-plane lattice matching, indium tin oxide (ITO) and yttria-stabilized zirconia (YSZ) were selected as underlying layers. We obtained (100)- and (001)/(010)-oriented films on ITO and YSZ, respectively. Ferroelastic domain formation was confirmed for both films by X-ray diffraction using the superlattice diffraction that appeared only for the orthorhombic symmetry. The formation of ferroelastic domains is believed to be induced by the tetragonal–orthorhombic phase transition upon cooling the films after deposition. The present results demonstrate that the orientation of HfO2-based ferroelectric films can be controlled in the same manner as that of ferroelectric films composed of conventional perovskite-type material such as Pb(Zr, Ti)O3 and BiFeO3.

Growth of (111)-oriented epitaxial and textured ferroelectric Y-doped HfO2 films for downscaled devices

In this study, the growth of (111)-oriented epitaxial and textured YO1.5-HfO2 (0.07:0.93 ratio) films using the pulsed laser deposition method is presented. Epitaxial films were prepared on ITO//(111)yttria-stabilized zirconia (YSZ) substrates (ITO: Sn-doped In2O3; YSZ: yttria-stabilized zirconia), while textured films were prepared on (111)Pt/TiOx/SiO2//Si substrates with and without an ITO buffer layer via the grain on grain coherent growth. Inserting an ITO layer increased the volume fraction of the ferroelectric orthorhombic phase. Both the epitaxial and uniaxially textured films exhibited similar ferroelectricity with a remanent polarization of around 10u2009μC/cm2 and a coercive field of 1.9 to 2.0 MV/cm. These results present us with a way of obtaining stable and uniform ferroelectric properties for each grain and device cells consisting of a small number of grains. This opens the door for ultimately miniaturized ferroelectric devices, such as ferroelectric field effect transistors with small gate leng...

Formation of (111) orientation-controlled ferroelectric orthorhombic HfO2 thin films from solid phase via annealing

0.07YO1.5-0.93HfO2 (YHO7) films were prepared on various substrates by pulse laser deposition at room temperature and subsequent heat treatment to enable a solid phase reaction. (111)-oriented 10 wt.u2009% Sn-doped In2O3(ITO)//(111) yttria-stabilized zirconia, (111)Pt/TiOx/SiO2/(001)Si substrates, and (111)ITO/(111)Pt/TiOx/SiO2/(001)Si substrates were employed for film growth. In this study, X-ray diffraction measurements including θ–2θ measurements, reciprocal space mappings, and pole figure measurements were used to study the films. The film on (111)ITO//(111)yttria-stabilized zirconia was an (111)-orientated epitaxial film with ferroelectric orthorhombic phase; the film on (111)ITO/(111)Pt/TiOx/SiO2/(001)Si was an (111)-oriented uniaxial textured film with ferroelectric orthorhombic phase; and no preferred orientation was observed for the film on the (111)Pt/TiOx/SiO2/(001)Si substrate, which does not contain ITO. Polarization–hysteresis measurements confirmed that the films on ITO covered substrates had s...

Thermally stable dielectric responses in uniaxially (001)-oriented CaBi4Ti4O15 nanofilms grown on a Ca2Nb3O10-nanosheet seed layer

To realize a high-temperature capacitor, uniaxially (001)-oriented CaBi4Ti4O15 films with various film thicknesses were prepared on (100)cSrRuO3/Ca2Nb3O10− nanosheet/glass substrates. As the film thickness decreases to 50u2009nm, the out-of-plane lattice parameters decrease while the in-plane lattice ones increase due to the in-plane tensile strain. However, the relative dielectric constant (εr) at room temperature exhibits a negligible degradation as the film thickness decreases to 50u2009nm, suggesting that εr of (001)-oriented CaBi4Ti4O15 is less sensitive to the residual strain. The capacitance density increases monotonously with decreasing film thickness, reaching a value of 4.5u2009μF/cm2 for a 50-nm-thick nanofilm, and is stable against temperature changes from room temperature to 400u2009°C irrespective of film thickness. This behaviour differs from that of the widely investigated perovskite-structured dielectrics. These results show that (001)-oriented CaBi4Ti4O15 films derived using Ca2Nb3O10− nanosheets as seed layers can be made candidates for high-temperature capacitor applications by a small change in the dielectric properties against film thickness and temperature variations.

Surface-segregation-induced phase separation in epitaxial Au/Co nanoparticles: Formation and stability of core-shell structures

We have studied formation and stability of core-shell structures in epitaxial Au/Co nanoparticles (NPs) by using atomic-resolution scanning transmission electron microscopy. As the particle size reduces, number of NPs having Au-shell increases and their frequency of occurrence reached 65%. Au segregation proceeds during particle growth at 520 K. The core-shell structure formation is particle size-dependent; the critical diameter dividing the Au-shell and the Co-shell structures is about 11 nm, below which the Au-shell is stable. After annealing at 800 K for 3.6 ks, Au-shell NPs were conserved while the Co-shell NPs changed to two-phase structures with a planar interface separating Au and Co. There is a local energy minimum where the Co-shell NP is metastable in the as-deposited state. A simple model based on surface and interfacial energies suggests stability of Au-shell structures. Surface-segregation-induced phase separation in small NPs, due to low surface free energy of Au, will be responsible for the...

Orientation control of barium titanate films using metal oxide nanosheet layer

In the present work, we aim to achieve the preferred crystal orientation of chemical solution deposition (CSD)-derived BaTiO3 films on ubiquitous Si wafers with the assistance of Ca2Nb3O10 nanosheet (ns-CN) template layers. The ns-CN on platinized Si (Pt/Si) substrates aligned the BaTiO3(100) plane to the substrate surface, because of the favorable lattice matching of the ns-CN (001) plane. The CSD process in air required a high crystallization temperature of 900 °C for the preferred crystal orientation of BaTiO3(100) because of the BaCO3 byproduct generated during the combustion reaction of the precursor gel. The processing in vacuum to remove CO2 species enhanced the crystal orientation even at the crystallization temperature of 800 °C, although it can generate oxygen vacancies () that cause distorted polarization behavior under an applied field higher than approximately 150 kV/cm. The relative dielectric constant (er) of the (100)-oriented BaTiO3 film on the ns-CN-supported Pt/Si substrate (ns-CN/Pt/Si) was generally larger than that of the randomly oriented film on Pt/Si, depending on the degree of crystal orientation.

Atomic and nanoscale imaging of a cellulose nanofiber and Pd nanoparticles composite using lower-voltage high-resolution TEM

We have examined the advanced application of transmission electron microscopy (TEM) for the structural characterization of a composite of cellulose nanofiber (CNF) and palladium (Pd) nanoparticles. In the present study, we focused on electron-irradiation damage and optimization of high-resolution TEM imaging of the composite. The investigation indicates that the CNF breaks even under low-electron-dose conditions at an acceleration voltage of 200 kV. We then applied lower-voltage TEM at 60 kV using a spherical aberration corrector and a monochromator, in order to reduce electron-irradiation damage and improve the spatial resolution. The TEM observation achieved high-resolution imaging and revealed the existence of small Pd nanoparticles, around 2 nm in diameter, supported on the CNF. It is considered that the use of a monochromator in combination with spherical aberration correction contributed to the atomic and nanoscale imaging of the composite, owing to the improvement of the information limit under a lower-acceleration voltage.

Polarization switching behavior of one-axis-oriented lead zirconate titanate films fabricated on metal oxide nanosheet layer

For the application of electronic devices using ferroelectric/piezoelectric components, one-axis-oriented tetragonal Pb(Zr0.40Ti0.60)O3 (PZT) films with thicknesses of up to 1 µm were fabricated with the aid of a Ca2Nb3O10 nanosheet (ns-CN) template for preferential crystal growth for evaluating their polarization switching behavior. The ns-CN template was supported on ubiquitous silicon (Si) wafer by a simple dip coating technique, followed by the repetitive chemical solution deposition (CSD) of PZT films. The PZT films were grown successfully with preferential crystal orientation of PZT(100) up to the thickness of 1020 nm. The (100)-oriented PZT film with ~1 µm thickness exhibited unique polarization behavior of ferroelectric polarization, i.e., a marked increase in remanent polarization (P r) up to approximately 40 µC/cm2 induced by domain switching under high electric field, whereas the film with a lower thickness showed only a lower P r of approximately 11 µC/cm2 even under a high electric field. The ferroelectric property of the (100)-oriented PZT film after domain switching on ns-CN/Pt/Si can be comparable to those of (001)/(100)-oriented epitaxial PZT films.

Characterization of (111)-oriented epitaxial (K0.5Na0.5)NbO3 thick films deposited by hydrothermal method

(111)-oriented epitaxial (K0.5Na0.5)NbO3 films of 2 µm thickness were deposited at 240 °C on (111) c SrRuO3//(111)SrTiO3 substrates by a hydrothermal method. Scanning transmission electron microscopy-energy-dispersive X-ray spectroscopy (STEM-EDS) mapping revealed that a K-rich interfacial region existed in the obtained films. Although the as-deposited films were annealed between 240 and 600 °C in O2 atmosphere, the crystal structure did not markedly change. On the other hand, the leakage current density drastically decreased from 10−2–100 to 10−6 A/cm2 at ±80 kV/cm after annealing above 240 °C. In addition, the relative dielectric constant (er), remanent polarization (P r), and piezoelectric constant (d 33,PFM) increased with increasing annealing temperature from 300 to 600 °C, and their values were respectively 840, 5.7 µC/cm2, and 64 pm/V for the films annealed at 600 °C.